Allocation of Ambipolar Charges on an Organic Diradical with a Vinylene–Phenylenediyne Bridge

Mayorga-Burrezo, Paula; Bejarano, Francesc; Calbo, Joaquín; Zhao, Xiaotao; De Sousa, J. Alejandro; Lloveras, Vega; Bryce, Martin R.; Ortí, Enrique; Veciana, Jaume; Rovira, Concepció; Crivillers, Núria

Abstract

Two redox and magnetically active perchlorotriphenylmethyl (•PTM) radical units have been connected as end-capping groups to a bis(phenylene)diyne chain through vinylene linkers. Negative and positive charged species have been generated, and the influence of the bridge on their stabilization is discussed. Partial reduction of the electron-withdrawing •PTM radicals results in a class-II mixed-valence system with the negative charge located on the terminal PTM units, proving the efficiency of the conjugated chain for the electron transport between the two terminal sites. Counterintuitively, the oxidation process does not occur along the electron-rich bridge but on the vinylene units. The •PTM radicals play a key role in the stabilization of the cationic species, promoting the generation of quinoidal ring segments.

Citation

Mayorga-Burrezo, P., Bejarano, F., Calbo, J., Zhao, X., De Sousa, J. A., Lloveras, V., Bryce, M. R., Ortí, E., Veciana, J., Rovira, C., & Crivillers, N. (2021). Allocation of Ambipolar Charges on an Organic Diradical with a Vinylene–Phenylenediyne Bridge. Journal of Physical Chemistry Letters, 12(26), 6159-6164. https://doi.org/10.1021/acs.jpclett.1c01565

• Journal Article Type: Article
• Acceptance Date: Jun 21, 2021
• Online Publication Date: Jun 29, 2021
• Publication Date: Jul 8, 2021
• Deposit Date: Dec 20, 2021
• Publicly Available Date: Jun 29, 2022
• Journal: Journal of Physical Chemistry Letters
• Electronic ISSN: 1948-7185
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 12
• Issue: 26
• Pages: 6159-6164
• DOI: https://doi.org/10.1021/acs.jpclett.1c01565
• Public URL: https://durham-repository.worktribe.com/output/1218530